Chlorinated derivatives of alkylene polyamines



Patented Nov. 2 9, 1949 unass- UNITED STATES PATENT 1 OFFICE OHLORINATEDDERIVATIVES F ALKYLENE POLYAMINES Frederick C. Bersworth, Verona, N. J.

No Drawing.

6 Claims.

This invention relates to new chemical compounds which are derivativesof alkylene or polyalkylene polyamines and which contain one or twochlorinated benzene radicals in the molecule. These compounds I havefound to be useful as bactericides and more particularly as bactericideshaving polyvalent metal sequestering action.

Chlorinated aromatic compounds containing a Application August 5, 1947Serial No. 766,469

benzenoid nucleus are known to be useful bacter- R-N-allrylene-Nalkylene -N-R wherein R is a member of the group consisting of-'-CH:COOM,

c1 c1 c1 c1 Q01, and CHQC1 01 l 1 not more than one R group beingCH2COOM, n is zero or a positive integer, alkylene is an alkylene groupcontaining not more than four carbon atoms, and M is a member of thegroup consisting of alkali metal and hydrogen.

The compounds of the present invention may be prepared in any of severaldifierent ways. In general the process of making the products hereindescribed is a two-step process. The first step preferably consists inreacting an amine with a suitable halogenated compound to form anintermediate product, the intermediate product containing at least twoamino nitrogen atoms. The second step consists in replacing the hydrogenatoms on the amino nitrogen atoms with acetic acid groups. Dependingupon the original starting materials, the intermediate or, final productmay or may not be chlorinated. The first step may be carried out bycondensing an aryl amine or an aralkyl amine with an aliphatic compoundin which either one or both terminal car n atoms are bonded to a halogenatom. Alternatively this condensation may take place bet een an aralkylcompound having a halogen atq attached to the terminal carbon of thealkyl group and a polyamine. The aryl group may or may not behalogenated at the time of this intermediate reaction. The intermediateproduct may then be reacted according to my U. S. Patent 2,407,645, r tothe chloracetic acid process, to replace w th acetate groups thehydrogen atoms remaining on the amino nitrogen atoms. These processes,and modifications thereof, for making the compounds of this inventionwill be illustrated in the examples which follow.

Example I One molar equivalent of pentachlor aniline is condensed withone molar eouivalent of l-chlor 2 amino ethane (ClCHzCHaNI-Iz) byheating the two together under substantially anhydrous conditions. Theresulting product pentachlor phenyl ethylene diamine hydrochloridecrystallizes out, is treated with NaOH to liberate the free base, and isthen reacted with sodium cyanide, formaldehyde and sodium hydroxideaccording to my U. S. Patent 2,407,645 to yield a crystallizablecompound believed to have the formula:

01 c1 CHzCOONa CHzCOONa Cl N-CHzCHrIL' The l-chlor 2 amino ethane may bemade according to the procedure reported by Seitz B. 24, 2626.

Example II Two molar equivalents of pentachlor aniline are condensedwith one molar equivalent of di- (p-chlor ethyl) amine by heating thetwo together. The hydrochloride salt which crystallizes out is treatedwith caustic to set free the base. The resulting crystalline producthaving the formula Cl Cl c1 01 and termed sym. di(pentachlor phenyl)diethylene triamine is reactedas in Example I according to my U. S.Patent 2,407,645 to yield a crystallizable compound believed to have theformula:

cmcooNa CHICOONa crncoom Cl 01 c1 c1 c1 N-CHaCH -N-CHzCHz-N c1 ExampleIII Two molar aquivalents of pentachlor aniline are reacted according toconventional procedure 1. e. by mixing and heating together with onemolar equivalent of ethylene dichloride. -The product crystallizing outis the intermediate product as the hydrochloride. The free base isliberated with caustic. The resulting product is then reacted as inExample I according to my U. S. Patent 2,407,645 to yield acrystallizable compound believed to have the formula:

c1 c1 c1 c1 ClQNCHaCHz-NCl 1 c1 c1 c1 CHzCOONa CHzCOONa Example 'IV Onemolar equivalent of pentachlor benzyl bromide is reacted by heating andmixing with a molar equivalent of diethylene triamine.

After treating with caustic, the resulting prodnot is reacted withsodium cyanide, formaldehyde and sodium hydroxide to yield acrystallizable product having the formula:

C1 C1 CHzC O ONa Similarly other alkylene chlorides, and polyamines maybe reacted with aryl amines or arylalkyl chlorides to form the compoundsof this invention. It is generally preferred to react fully chlorinatedaryl groups to form the intermediate product but if chlorination is tobe performed it is preferred that the reaction wherein the acetategroups replace the hydrogen atoms on the nitrogen atoms be carried outbefore chlorination of the intermediate product. However, it is entirelypossible to first chlorinate the intermediate product although the yieldof desired product may be inferior.

Among the general characteristics of the compounds of this invention arethat they are excellent bactericides in general and particularly in thepresence of hard water and soap. The compounds disclosed above aregenerally yellowish colored crystalline salts which are soluble inwater, and in dilute alcohol solutions. They have an iso-electric pointof between 1.2 and 1.8. The

compounds may be thought of as containing solubilizing groups (theacetate groups) and "non-solubilizing groups (the aryl groups). In thosecompounds containing multiple solubilizing groups and only a singlenon-solubilizing group the solubility in water is quite marked. In thosecompounds containing a lower ratio of "solubilizing to non-solubilizinggroups the solubility is decreased, although still appreciable.

If copper in ionic form is added to an aqueous solution of one of thecompounds of this invention, a copper complex is apparently formed which-is soluble in water. This complex has been found to be an excellentfungicide, and may be added to hard water in the presence of soapwithout the formation of a curdy precipitate.

The importance of the elimination of a hard water flock in the presenceof a strong alkali or soap is great. It has been shown that upon theformation of a hard water flock, whether as the result of the formationof calcium hydroxide or calcium (or magnesium) soap, bacteria areprotected. A medium apparently bacteria-free after treatment withphenol, and having a flock 5 of calcium soap, was filtered, theprecipitate was thoroughly washed with sterile water and added tobacteria free serum. The bacteria became active again. The compoundsdescribed herein eliminate any possibility of any contaminated l flock.

I claim: ,1. A compound represented by the formula:

R-N-alkylene (-N-alkylene N-R tmooom cmooom omoboM wherein R is a memberof the group consisting of c1 c1 c1 c1 -omoo0m,@o1, and -CH 01 1 1 c1 1not more than one B group being CH:COQM.

n is one of the group consisting of zero and a positive integer,alkylene is an alkylene group containing not more than four carbonatoms, and M is a member of the group consisting of alkali metal andhydrogen.

2. A compound according to claim 1 wherein each R is 3. A compoundrepresented by the formula c1 c1 c1 N-CH:CHr-NCH:COON&

c1 c1 cmoooNs HaCOONa' 4. A compound represented by the formula 0 c1 c1Q 01 CHrN-CH -CH:(NCHrCH:)N-CHzCOONI c 1 omoooNa dmooom 3,0001%- 5. Acompound according to claim 1 wherein REFERENCES CITED The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,168,181 Ulrich et a1. Aug. 1,1939 2,387,976 Bersworth Oct. 30, 1945 2,413,856 Bersworth Jan. '7, 19472,428,353 Bersworth Oct. 7, 1941

